EP3087047B1 - Procédé de déshydratation de l'éthanol catalysé par un acide - Google Patents

Procédé de déshydratation de l'éthanol catalysé par un acide Download PDF

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EP3087047B1
EP3087047B1 EP14816268.8A EP14816268A EP3087047B1 EP 3087047 B1 EP3087047 B1 EP 3087047B1 EP 14816268 A EP14816268 A EP 14816268A EP 3087047 B1 EP3087047 B1 EP 3087047B1
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ethanol
nitrogen
feedstock
ethanol feedstock
stream
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EP3087047A2 (fr
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Leslie William Bolton
Nigel Stewart BROWN
Lewis Adam HEPTONSTALL
Andrew John HOGBEN
Susan Elizabeth LITTLE
Stephen James Smith
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Technip Energies NV
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Technip E&C Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C07C29/82—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by azeotropic distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/94—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/08—Ethanol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/46—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/06—Diethyl ether
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/20—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to processes for the acid-catalysed dehydration of ethanol, for example a process for producing ethylene and/or diethyl ether by the vapour phase dehydration of ethanol using a heteropolyacid catalyst such as silicotungstic acid.
  • Ethanol is widely used commercially as a gasoline additive or as a fuel per se, as a solvent, as a germicide, as an antifreeze, as a component in the food and beverage industry, and as a chemical feedstock. It is particularly useful as a feedstock for acid-catalysed reactions such as the dehydration to ethylene. See e.g. WO 2008/138775 which discloses a process for the dehydration of one or more alcohols comprising contacting the one or more alcohols with a supported heteropolyacid catalyst in the presence of one or more ethers; and WO 2008/062157 which discloses a heteropolyacid catalyst and the use thereof in a process for the production of olefins from oxygenates.
  • Ethanol is of increasing significance as a chemical feedstock, since it is readily obtainable from biological sources, in particular by the fermentation of sugars and/or biomass. Ethanol from biological sources, so-called bio-ethanol, thus provides one way of reducing the dependence on crude oils for fuel uses and as chemical feedstocks.
  • Ethanol particularly bio-ethanol (or ethanol obtained by fermentation) typically contains low levels of nitrogen-containing contaminants.
  • One possible source of nitrogen-containing contaminants may be ammonia which may be introduced during the fermentation stage. Once in the process, the ammonia can react with ethanol and other impurities to form a variety of nitrogen-containing compounds.
  • nitrogen-containing contaminants in ethanol is undesirable since these compounds may interfere with subsequent chemical processing in which the ethanol is used as a feedstock.
  • nitrogen-containing contaminants which may be volatile nitrogen compounds such as acetonitrile and ammonia, and particularly acetonitrile, can poison, deactivate or otherwise interfere (e.g. act as a precursor to a catalyst poison) with a number of catalysts which may be used in the processing of alcohol feedstocks, for example by neutralising acidic sites on heterogeneous acidic catalysts. This may lead to a loss of process efficiency and a need to undesirably replace the catalyst more frequently.
  • Approaches have been taken to reduce the level of acetonitrile in ethanol feedstocks, with such approaches including aqueous extraction, sacrificing acid and adsorption.
  • WO 1997/045392 discloses a process for the production of ethers in which deactivation of an acidic ion-exchange resin etherification catalyst is reduced by separating nitriles from an olefin feedstock by aqueous extraction. The nitriles are subsequently separated into an alcohol phase and hydrogenated to form amines which are more easily separable from the alcohol phase by fractionation.
  • EP 1 176 132 A1 discloses a process for preparing ethers comprising reacting an alcohol and an olefin in the presence of an acidic catalyst. Excess alcohol is recycled to the reaction zone together with nitrile compounds originating from the olefin feed. To avoid accumulation of nitriles in the system and deactivation of the catalyst, the excess alcohol comprising nitrile compounds is contacted in the liquid phase with a solid acid prior to being recycled to the reaction zone. It is reported that this reduces the level of nitrites in the recycled alcohol stream by at least 50 %.
  • WO 2010/060981 discloses a process for the purification of an alcohol in the course of a process for the preparation of olefins by acid-catalysed dehydration of the alcohol, the process comprising contacting the alcohol with one or more adsorbent materials. It is disclosed in WO 2010/060981 that while ammonia and amines can be adsorbed, nitrile impurities such as acetonitriles must be hydrogenated to provide modified impurities which are more readily adsorbed. Thus, according to WO 2010/060981 , the alcohol feed is subjected to a hydrogenation step prior to contacting the alcohol with the one or more adsorbent materials.
  • the Examples of WO 2010/060981 teach the removal of basic compounds from bio-ethanol by adsorption on a sulfonic acid resin at ambient temperature and pressure.
  • WO 2011/089235 discloses a process for the dehydration of an alcohol having at least two carbon atoms to make the corresponding olefin comprising contacting a stream comprising the alcohol with a catalyst which is a crystalline silicate of the group FER, MWW, EUO, MFS or TON having Si/Al under 100, or a dealuminated or phosphorus modified derivative thereof.
  • US 5,415,741 discloses the separation of ethanol from isopropanol by azeotropic distillation using azeotropic distillation agents such as acetonitrile and methylene chloride.
  • EP 0053917 discloses a process for purifying crude ethanol to produce a pure ethanol-water azeotrope using only two distillation columns and high pressure, low reflux ratio distillation conditions.
  • the present invention relates to a process for the acid-catalysed dehydration of ethanol, the process comprising the steps of:
  • Also disclosed herein is a process for the preparation of an ethanol feedstock for the acid-catalysed dehydration of ethanol to ethylene, the process comprising the step of distilling an ethanol feedstock comprising at least one nitrogen-containing contaminant wherein the distillation has a reflux ratio of at least 20: 1 and the ethanol feedstock exits the distilling step in a bottom stream.
  • the present invention relates to use of a process according to the first aspect to dehydrate a nitrogen-containing contaminant-depleted, preferably acetonitrile-depleted, ethanol feedstock in the presence of an acid catalyst.
  • the present disclosure also provides use of the process of the first aspect to react a non-condensable gas depleted, preferably an oxygen, carbon dioxide, carbon monoxide and/or nitrogen depleted, ethanol feedstock in the presence of an acid catalyst.
  • the present disclosure also relates to products obtainable, preferably obtained, from a process according to the first aspect.
  • Figure 1 shows a schematic representation of a process according to the present invention.
  • the present invention provides processes for the acid-catalysed dehydration of ethanol and particularly to methods involving the purification of the ethanol feedstock before reacting it in the presence of an acid catalyst.
  • the ethanol feedstock used in the present process can in principle be from any source, but preferably comprises bio-ethanol or is a bio-ethanol feedstock.
  • an ethanol feedstock refers to a composition which comprises at least about 50% ethanol.
  • an ethanol feedstock to be treated according to the process of the present invention is an ethanol feedstock comprising at least about 70 wt% ethanol, more preferably at least about 80 wt% ethanol, even more preferably at least about 85 wt% ethanol and even more preferably still at least about 90% ethanol.
  • the ethanol feedstock is, or comprises, bio-ethanol.
  • the ethanol feedstock may additionally comprise an inert component, wherein said inert component is any component which does not react with ethanol or adversely affect the distillation step under the conditions used and would not adversely affect a process for the acid-catalysed reaction of ethanol, e.g. the dehydration of ethanol to ethylene and/or diethyl ether.
  • the inert component may be selected from saturated hydrocarbon compounds having from 1 to about 10 carbon atoms, napthenes, and inert gases such as nitrogen.
  • the ethanol feedstock may comprise a single type of alcohol (i.e. just ethanol), or it may comprise a mixture of two or more different alcohols (e.g. ethanol plus at least one further alcohol).
  • the alcohols present in the ethanol feedstock are substantially ethanol, for example at least about 95 wt% of the alcohols present in the ethanol feedstock is ethanol, preferably at least about 98 wt%, such as at least about 99 wt% or at least about 99.5 wt%, of the alcohols present in the ethanol feedstock is ethanol.
  • the ethanol feedstock comprises ethanol produced from a biological source (bio-ethanol), for example by fermentation of biomass and/or a derivative thereof.
  • biomass refers to any biological source of a carbohydrate which may be converted to an alcohol by fermentation of the biomass directly or fermentation of a derivative of the biomass; for example biological sources of sugars, starches and cellulose.
  • bio-ethanol may be obtained by the fermentation of sugars from sources such as sugar beet, sugar cane, molasses or corn syrup.
  • bio-ethanol may be obtained by fermentation of feedstocks derived from sugar cane, such as sugar cane molasses and sugar cane juice; sugar beet, such as sugar beet molasses and sugar beet juice; cereal crops, such as corn or wheat derived feedstocks like corn syrup; and lignocellulosic materials, such as fast growing grasses or "energy grasses".
  • sugar cane such as sugar cane molasses and sugar cane juice
  • sugar beet such as sugar beet molasses and sugar beet juice
  • cereal crops such as corn or wheat derived feedstocks like corn syrup
  • lignocellulosic materials such as fast growing grasses or "energy grasses”.
  • the ethanol feedstock may comprise water.
  • the ethanol feedstock may be a hydrous ethanol composition, e.g. one which has not been dried beyond the ethanol-water azeotrope composition.
  • Such hydrous ethanol compositions may be the raw or crude ethanol composition which results from the production of an ethanol product which has been obtained by the fermentation of biomass without further subjecting the obtained ethanol to a dewatering step that dries the composition beyond the ethanol-water azeotrope.
  • Such hydrous ethanol compositions may contain an amount of water which is equal to or greater than the amount of water which is determined by the azeotrope of the ethanol-water composition.
  • a hydrous ethanol composition includes also those to which water has been added, for example, an ethanol or bio-ethanol composition to which from 0.01 % to 5% water, preferably from 0.5% to 4%, more preferably from 1% to 3% and even more preferably from 1.5% to 2.5%, such as 2%, water has been added, all by weight of the ethanol composition.
  • the ethanol feedstock may comprise an organic acid such as acetic acid.
  • the acetic acid present in the ethanol feedstock may be from about 10ppb to about 1000ppm, preferably from about 1ppm to about 500ppm, more preferably from about 10ppm to about 300ppm, even more preferably from about 50ppm to about 200ppm, and even more preferably still from about 70ppm to about 150ppm, such as about 100ppm, by weight.
  • Any of the amounts of water added disclosed above may be added in combination with the acetic acid ranges described above, or differing levels of water may be added, such as from 0.7% to 1 0%, preferably from 1.2% to 7%, and more preferably from 1.8% to 5%, by weight.
  • a distillation comprising additional water and/or organic acid (especially acetic acid) may be operated without adherence to the reflux ratios described herein.
  • the ethanol feedstock may be an anhydrous ethanol composition, i.e. composed of anhydrous alcohol.
  • anhydrous ethanol compositions may contain an amount of water which is less than the amount of water which is determined by the azeotrope of the ethanol-water composition.
  • an anhydrous ethanol composition may be at least about 95% ethanol, preferably at least about 98% ethanol, more preferably at least about 99% ethanol and even more preferably at least about 99.5% ethanol.
  • anhydrous it is understood and accepted that the remainder of the composition besides the ethanol may comprise water, or be substantially water.
  • concentration of nitrogen-containing contaminants in the ethanol feedstock to be treated according to the process of the present invention will generally be at a level which is detrimental to the performance of an acid catalyst, such as a supported heteropolyacid catalyst.
  • concentrations of nitrogen-containing contaminants are usually reported as parts per million by weight (ppmw) of the total nitrogen content of said nitrogen-containing contaminants. References herein to ppmw of nitrogen shall be interpreted as ppmw of nitrogen in the form of nitrogen-containing contaminants. The ranges provided below may apply to the sum for all nitrogen-containing contaminants, to a subset of them, or to a particular example, such as acetonitrile.
  • the ethanol feedstock to be treated according to the process of the invention may comprise over 0.05 ppmw of nitrogen, preferably at least 0.2 ppmw of nitrogen, more preferably at least 0.25 ppmw of nitrogen, more preferably at least 0.3 ppmw of nitrogen, still more preferably at least 0.4 ppmw of nitrogen, and most preferably at least 0.5 ppmw of nitrogen.
  • the ethanol feedstock to be treated according to the process of the invention may comprise at least 0.6 ppmw, at least 0.7 ppmw, at least 0.8 ppmw, at least 0.9 ppmw or at least 1.0 ppmw of nitrogen.
  • the ethanol feedstock comprises 50 ppmw or less of nitrogen in accordance with the present invention.
  • the ethanol feedstock comprises 25 ppmw or less of nitrogen, more preferably 10 ppmw or less of nitrogen, more preferably 8 ppmw or less of nitrogen, for instance 6 ppmw or less of nitrogen, 4 ppmw or less of nitrogen, or 2 ppmw or less of nitrogen.
  • the levels of nitrogen-containing contaminants in the ethanol feedstock provided above may be applicable at the beginning of an overall process involving the distillation of the present invention (e.g.
  • a pre-treatment step may be carried out by any suitable technique, for instance by contacting the ethanol feedstock with an adsorbent as discussed below.
  • the concentration of nitrogen-containing contaminants in the ethanol feedstock to be treated according to the process of the invention may be determined by any suitable analytical technique known to persons of skill in the art. Suitable techniques include gas chromatography in conjunction with a nitrogen/phosphorus detector (GC-NPD), chemiluminescence methods and ion exchange chromatography. It has been found that GC-NPD is a particularly effective technique for observing individual nitrogen-containing species in the ethanol feedstock.
  • GC-NPD is a particularly effective technique for observing individual nitrogen-containing species in the ethanol feedstock.
  • the use of a nitrogen/phosphorus detector provides significantly enhanced signal strength for nitrogen compounds in comparison to carbon species (approximately 10 4 enhancement). As a result, nitrogen compounds are clearly visible in the GC chromatogram along with the signals for the alcohol and in some cases the corresponding dialkyl ether.
  • a suitable chemiluminescence technique may involve vaporising and oxidizing an ethanol feedstock, measuring the concentration of nitrogen oxides in the vaporized and oxidized ethanol feedstock by chemiluminescence and hence determining the concentration of nitrogen atoms in the ethanol feedstock from the measured concentration of nitrogen oxides.
  • Such techniques are described in further detail in US 4,018,562 and GB 2373856 .
  • the nitrogen-containing contaminants may include a number of different types of nitrogen-containing compounds, such as nitrogen-containing contaminants with a lower boiling point than ethanol, for instance volatile nitrogen compounds.
  • nitrogen-containing contaminants include nitriles (i.e. compounds containing one or more nitrile moiety, such as acetonitrile), amines (i.e.
  • amine compounds containing one or more amine moiety such as ammonia, methylamine, ethylamine, dimethylamine, diethylamine, triethylamine, trimethylamine, ethanolamine), ammonium cations, amides, imides and mixtures thereof; additionally, more complex and heterocyclic nitrogen-containing compounds, such as azines, diazines, pyrroles, diazoles, triazoles, tetrazoles and mixtures thereof, and more complex molecules containing one or more different nitrogen-containing moieties and optional other functional groups, such as amino acids, may also be present in the ethanol feedstock.
  • amine moiety such as ammonia, methylamine, ethylamine, dimethylamine, diethylamine, triethylamine, trimethylamine, ethanolamine
  • ammonium cations such as ammonia, methylamine, ethylamine, dimethylamine, diethylamine, triethylamine, trimethylamine, ethanol
  • Nitriles have low basicity due to the sp hybridization of the nitrogen atom which places the electron density of the nitrogen lone-pair close to the nitrogen nucleus, thus making the lone-pair relatively unreactive. Consequently, nitriles such as acetonitrile in particular pass through acidic adsorbents with substantially no adsorption at the concentrations typical in ethanol feedstocks, especially bio-ethanol. Nonetheless, nitriles are found to be capable of quantitatively deactivating acidic catalysts used for alcohol dehydration processes. It has previously been proposed to carry out a pre-treatment step to convert nitriles to amines by hydrogenation, as amines are more readily adsorbed.
  • the nitrogen-containing contaminant present in the ethanol feedstock comprises, or is, acetonitrile.
  • nitrogen-containing contaminants may be taken to refer to all nitrogen-containing contaminants, any subset of them (e.g. combination of those cited above), or any particular one (for example acetonitrile), as if simply replaced with the alternative terminology.
  • the processes according to the invention comprise the step of distilling an ethanol feedstock with a reflux ratio of at least 20:1 to form an overhead stream and a bottom stream.
  • the distillation may be performed in a conventional distillation column with a number of stages (e.g. ideal stages) commensurate with the reflux ratio required, for example between about 5 and about 50 ideal separation stages.
  • the feed point should generally be in the lower part of the column.
  • generally distillation columns have a reboiler, in this instance if the feed is pre-heated to contain at least a mixture of liquid and vapour this may be sufficient to provide enough heat to drive the required separation within the column.
  • the column is also usually fitted with an overhead condenser to condense the overhead vapour to provide the liquid reflux stream and to optionally allow the separation of the non-condensable components.
  • the acetonitrile is the distillate, or at least a portion of the distillate, or is at a higher concentration in the distillate than the treated ethanol or distillation bottoms), thus reducing the level in the ethanol stream used for further process steps, and therefore reducing the extent of catalyst deactivation when subsequent process steps utilise an acid catalyst.
  • an azeotropic mixture forms between ethanol (55 mol%) and acetonitrile (45 mol%) with a boiling point (72.8°C) which is lower than that of ethanol (78.31°C) (the quoted proportions and boiling points here being at atmospheric pressure).
  • this azeotropic effect is available even at very low concentrations of acetonitrile and thus enables removal of the nitrogen-containing contaminant by distillation overhead, reducing the energy required for the process step.
  • the level of acetonitrile is typically low (such as up to about 10ppm) in feedstock ethanol, the quantity of ethanol lost through the distillation is also small.
  • the applicants have found that a similar azeotropic effect also enables separation in the presence of water, i.e.
  • the distillation step is conducted with a reflux ratio of at least 20:1.
  • reflux ratio is the ratio of the rate of condensate returned to the distillation column (e.g. from the reflux stream) to the rate of condensate taken off (e.g. from the distillate stream) (by mass), so for example a ratio of 20:1 indicates 20 parts condensate returned to 1 part taken off.
  • the reflux ratios herein may be calculated on a mass basis.
  • the reflux ratio may be in the range of from 20:1 to 5000:1, preferably from 100:1 to 2000:1 and more preferably from 500:1 to 1500:1.
  • the distillation step may be carried out at a pressure of from 0.02 bara to less than 2 bara, preferably from 0.05 bara to 1.5 bara, more preferably from 0.1 bara to 1.0 bara and even more preferably from 0.2 bara to 0.6 bara.
  • azeotrope is maintained at reduced pressure and accordingly that, if desired, a distillation column with fewer stages may be used for the distillation step along with (if reboiler steam is being used) lower grade reboiler steam, which improves overall process efficiency.
  • the skilled person may select a suitable combination of reflux ratio, number of separation stages, location of the feed point and the state of the feed, i.e. liquid, heated liquid, vapour/liquid mixture, vapour or superheated vapour, in order to obtain desired levels of ethanol recovery and contaminant (e.g. acetonitrile) separation.
  • the reflux ratio may be in the range of from 100:1 to 1500:1 by mass, with between about 5 and about 50 ideal separation stages, with a feed point located in about the middle of the column and with the feed heated to approximately match the temperature of the liquid in the column at the feed point.
  • the treated ethanol feedstock i.e. the bottom stream from the distillation
  • distillation according to the present invention also acts to de-gas the ethanol feedstock, removing non-condensable gas components such as oxygen, carbon dioxide, carbon monoxide and nitrogen which can negatively impact the final product specification, for example by contaminating a product ethylene stream from an acid-catalysed dehydration of ethanol.
  • the distillation step may in principle occur at any stage after an ethanol feedstock is provided.
  • it may be an integral part of an ethanol or bio-ethanol production process.
  • Bio-ethanol production processes typically form a mash stream (approximately 10% mash in water) which is fed to a mash column to remove solids and water and then a rectifying column to remove water.
  • An optional drying step after rectifying may also be present, such as for example a molecular sieve or extractive distillation with ethylene glycol or another suitable material.
  • the distillation step may therefore be placed between the rectifying column and drying step or after the drying step.
  • the distillation step is separate to ethanol production, i.e. in the case of bio-ethanol production the distillation step occurs after the rectifying step in order to reduce the energy required to be provided to the distillation.
  • the distillation step may be a composite step, i.e. a step comprising multiple distillations.
  • Such a step of multiple distillations may comprise one or more distillations according to the present invention and may or may not be in combination with one or more further distillation steps having differing conditions, for example in order to target the removal of other contaminants besides the nitrogen-containing contaminants particularly addressed by the present invention.
  • distillation step may be followed by an adsorption step and then a further distillation step
  • a distillation step described below (with reference to Figure 1 ) including the reboiler may be followed by another such distillation step with or without the reboiler, or a distillation step may be directly followed by another distillation step. It would be recognised by one skilled in the art which stream should pass from one distillation step to the next in order to continue purifying the ethanol feedstock.
  • Further processing steps may appear as part of the present process after the distillation step and before the acid-catalysed reaction step.
  • acid-catalysed reactions of ethanol are often performed in the vapour phase.
  • the treated ethanol stream from the distillation step of the present invention is the bottom stream from the distillation column and may therefore be in the liquid phase, it may be desirable to evaporate the bottom stream before reacting it in the presence of an acid catalyst. It may also be desirable to change the pressure of the bottom stream from the distillation column or pass it through a liquid or vapour-phase guard bed. Accordingly, the treated ethanol feedstock resulting from the distillation may be fully or partially condensed and/or evaporated prior to feeding to the acid-catalysed reaction step of the process of the invention.
  • the bottom stream i.e. treated ethanol feedstock
  • an acid catalyst to form a product.
  • the acid catalysed reaction may be any reaction available, for example esterification or dehydration.
  • the acid catalysed reaction is a dehydration reaction, e.g. the dehydration of ethanol to ethylene and/or diethyl ether. Often, ethylene is the preferred product of such reactions.
  • the treated ethanol feedstock may conveniently pass from the distillation (e.g. a distillation column) to the acid-catalysed reaction (e.g. a catalytic reactor) via a reboiler/evaporator to bring the treated ethanol into the vapour phase.
  • the distillation e.g. a distillation column
  • the acid-catalysed reaction e.g. a catalytic reactor
  • the treated ethanol feedstock is in the vapour phase when it contacts the acid catalyst (e.g. dehydration catalyst).
  • the acid catalyst e.g. dehydration catalyst
  • This may be achieved by vaporising the treated ethanol feedstock prior to vapour phase acid-catalysed reaction (e.g. ethanol dehydration).
  • the temperature and pressure of the acid-catalysed reaction step may be greater or lower than the temperature and pressure of the treated ethanol feedstock resulting from the distillation step of the process according to the invention, thus the temperature and pressure of the treated ethanol feedstock may be adjusted prior to contacting the treated ethanol feedstock with the acid catalyst; alternatively, the temperature and pressure of the acid-catalysed reaction step in the present invention may be selected such that the treated ethanol feedstock resultant from the distillation step is at the same temperature and pressure as the acid-catalysed reaction step.
  • the reaction of the ethanol is acid-catalysed.
  • any acid or mixture of acids may be the catalyst for the further reaction.
  • the acid is suitable for use in heterogeneous catalysis.
  • acid catalysts include inorganic acids such as tungstic acid, sulphuric acid, phosphoric acid, hydrochloric acid and mixtures thereof.
  • the acid catalyst comprises, or is, a heteropolyacid, for example silicotungstic acid, silicomolybdic acid, phosphotungstic acid or phosphomolybdic acid. More preferably, the acid catalyst comprises, or is, silicotungstic acid.
  • the acid catalyst is an alcohol dehydration catalyst, such as an ethanol dehydration catalyst, and as such may be any of the alcohol dehydration catalysts or ethanol dehydration catalysts that are known in the art.
  • the acid catalyst may be, or comprise, a silicate, such as a crystalline silicate or zeolite, and may preferably be a crystalline silicate having a Si:Al ratio of at least 100, a dealuminated crystalline silicate or a phosphorous modified zeolite, for example as described in WO 2009/098262 .
  • the acid catalyst may be a heteropolyacid catalyst, for instance as described by WO 2008/138775 and WO 2008/062157 .
  • the acid catalyst is a heteropolyacid catalyst.
  • the heteropolyacid catalyst is preferably supported on a suitable inert support, such as silica or alumina.
  • Suitable conditions for acid-catalysed reactions of ethanol are well-known in the art and to the skilled person, for instance with reference to the prior art documents cited herein.
  • typical reaction conditions include a temperature of from about 280°C to about 500°C, a total pressure of from about 0.5 bara to about 30 bara, and a partial pressure of alcohol (or ethanol) that is preferably from about 1.2 bara to about 4 bara.
  • typical reaction conditions include a temperature of from about 180°C to about 270 °C and a pressure of from about 1 bara to about 45 bara.
  • An olefin product may be recovered and may subsequently be used in a wide range of industrial applications as known in the art, for instance in the preparation of polymers and oligomers (and/or precursors thereof), as components of fuels and lubricants and in the preparation of surfactants.
  • the present invention may provide a polymeric product obtained by polymerisation of olefins produced according to the processes of the present invention, an oligomeric product obtained by oligomerisation of olefins produced according to the invention, fuel and lubricant compositions comprising said olefins and/or said oligomeric or polymeric products, and surfactant compositions comprising said olefins and/or said oligomeric or polymeric products.
  • the ethanol feedstock may be subjected to additional treatment steps to lower or manage the levels of one or more specified or unspecified nitrogen-containing or other contaminants, such as treatment with an adsorbent material (e.g. in a liquid or vapour phase guard bed) or any of the other techniques known in the art and/or referenced herein, such as disclosed in WO1997/045392 , EP1176132A1 or US6770790 .
  • additional steps may appear before and/or after the distillation step according to the present process, or in between distillation steps if multiple distillation steps are used.
  • the adsorbent which may be used for the treatment of the ethanol feedstock in the liquid or vapour phase may be any adsorbent capable of adsorbing nitrogen-containing compounds and that is stable under the conditions at which the ethanol feedstock is brought into contact with it.
  • the adsorbent used for the treatment of the ethanol feedstock is a porous solid acidic adsorbent.
  • adsorbent materials include aluminosilicates such as zeolites, silica-alumina; silicates; silicas; aluminates; aluminas such as activated aluminas; molecular sieves; carbon-based adsorbent materials such as activated carbons (particularly for liquid phase usage); clays (particularly for liquid phase usage); resins, for example strong acid ion exchange resins such as sulphonic acid resin; and aluminophosphates.
  • aluminosilicates such as zeolites, silica-alumina; silicates; silicas; aluminates; aluminas such as activated aluminas; molecular sieves; carbon-based adsorbent materials such as activated carbons (particularly for liquid phase usage); clays (particularly for liquid phase usage); resins, for example strong acid ion exchange resins such as sulphonic acid resin; and aluminophosphates.
  • the adsorbent may optionally be treated or impregnated with an acid, such as phosphoric acid, phosphonic acid, sulfuric acid or a sulphonic acid, and/or may optionally be modified with a transition metal.
  • the adsorbent is selected from the group consisting of zeolites, silica-aluminas and mixtures thereof.
  • the adsorbent material may be used individually or in admixture with other adsorbent materials and/or inert materials, and so for example an adsorption step may be carried out in both the liquid phase and the vapour phase with either adsorption step preceding the other.
  • the temperature, pressure and space velocities at which the ethanol feedstock contacts the adsorbent may be selected to be suitable for the phase of the ethanol feedstock desired and adsorbent material used.
  • the adsorption may be carried out by passing the ethanol feedstock in the vapour phase through a fixed bed, fluidised bed or moving bed of the adsorbent.
  • liquid phase adsorption may be carried out through a fixed bed.
  • Multiple adsorption zones may also be used in this step, wherein each adsorption zone may contain the same or different adsorbents and may be operated at the same or different conditions.
  • One particular example of the use of multiple adsorption zones comprises treating the ethanol feedstock in a system comprising at least two adsorption zones, wherein at least one adsorption zone is operating under conditions such that the ethanol feedstock is contacted with an adsorbent in the liquid phase and at least one adsorption zone is operating under conditions such that the alcohol composition is contacted with an adsorbent in the vapour phase.
  • Any steps within the processes of the present invention may be operated as continuous or batch process, preferably as continuous processes.
  • FIG. 1 a schematic of a process according to the present invention is provided, wherein an ethanol feedstock in feed stream 101 is provided to a distillation column 201.
  • the feed stream 101 may be heated, e.g. to match the temperature of the liquid in the column at the feed point.
  • the distillation column forms at least an overhead stream 102 and a bottom stream 103, each having a respective exit point.
  • the bottom stream may be greater than about 95% of the feed mass rate, preferably from about 98% to about 99.9999% of the feed mass rate.
  • the feed point for the ethanol feedstock may be positioned intermediate between the exit points of the overhead stream 102 and the bottom stream 103.
  • the overhead stream 102 is passed to a condenser 202 (which may be any type of condenser e.g. a conventional condenser as known in the art) forming a condensed stream 104 and a gaseous stream 105. At least a portion (reflux stream 106) of the condensed stream 104 is recycled into the distillation column 201 to provide reflux liquid to the column. The remainder (distillate stream 107) may be passed to further steps 203 (not shown schematically), for example other uses (e.g. as fuel-grade ethanol) or disposal as waste.
  • the reflux ratio is therefore the ratio of the rate of reflux stream 106 returned to the distillation column 201 to the rate of distillate stream 107 taken off to further steps 203.
  • the distillate stream 107 may be very small, for example less than about 5% of the feed mass rate, preferably from about 0.0001% to about 2% of the feed mass rate.
  • the gaseous stream 105 may be disposed of as waste or otherwise captured 204 (not shown schematically), for example by optionally passing the gaseous stream to a vent condenser to minimise the release of volatile organic compounds to the atmosphere.
  • the bottom stream 103 is the treated ethanol feedstock. Bottom stream 103 may be passed to an optional reboiler 205 resulting in an evaporated stream 108 and a product stream 109.
  • the evaporated stream 108 may be recycled into the distillation column 201 to provide vapour and heat to the distillation column 201.
  • the product stream 109 may be passed to the acid-catalysed reaction according to the present invention (206, not shown schematically) directly or via further processing steps (e.g. as detailed herein).
  • bottom stream 103 may be passed to the acid-catalysed reaction step directly or via further processing steps, for example those highlighted herein.
  • the distillation column can offer improved energy efficiency by heat exchanging the product stream 109 with the feed stream 101.
  • Other heat integration options with upstream and downstream processes could be considered. Examples include, but are not limited to:
  • the present disclosure also relates to a process for the preparation of an ethanol feedstock for the acid-catalysed dehydration of ethanol to ethylene, the process comprising the step of distilling an ethanol feedstock comprising at least one nitrogen-containing contaminant wherein the distillation has a reflux ratio of at least 20:1, especially wherein the ethanol feedstock exits the distilling step in a bottom stream.
  • the present invention provides a use of a process according to the first aspect to dehydrate a nitrogen-containing contaminant-depleted, preferably acetonitrile-depleted, ethanol feedstock in the presence of an acid catalyst.
  • the present disclosure also provides a use of a process according to the first aspect to dehydrate a non-condensable gas depleted, preferably an oxygen, carbon dioxide, carbon monoxide and/or nitrogen depleted, ethanol feedstock in the presence of an acid catalyst.
  • the present disclosure also provides products obtainable from, preferably obtained from, a process according to the first aspect, especially a product comprising ethylene and/or diethyl ether in respect of the first aspect.
  • Example Details 100 wt% bio-ethanol 1 2 98 wt% bio-ethanol 1 / 2 wt% water 3 95.5 wt% bio-ethanol 1 / 4.5 wt% water 4 bio-ethanol 1 with 100 ppm acetic acid 5 95.5 wt% bio-ethanol 1 / 4.5 wt % water with 100 ppm acetic acid 1 Bio-ethanol sample contained 8.5 ppm nitrogen by mass of which 850 ppb was acetonitrile.
  • a 2 L, three-necked, round bottom flask was used as the reservoir, with 20 trays (10 theoretical stages) of 1" diameter glassware making up the distillation column.
  • a thermocouple was placed in the reservoir and at the take-off point to allow temperature measurement at both places.
  • the take-off point itself had a hold-up volume of ca. 10 mL, filled by closing a Young's tap on a bypass. This was left open, except immediately before (i.e. 2 - 3 minutes before) samples were collected off the top.
  • the reservoir was charged with the example to be studied and a sample of this example taken.
  • a heating mantle (520 W) contacting the reservoir was put on full power and the distillation apparatus left until the column was refluxing vigorously.

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Claims (13)

  1. Procédé de déshydratation d'éthanol catalysée par un acide, le procédé comprenant les étapes qui consistent à :
    (a) distiller une charge d'alimentation constituée d'éthanol (101) comprenant au moins un contaminant contenant de l'azote pour former un flux de tête (102) et un flux de fond comprenant de l'éthanol (103), dans lequel la distillation a un taux de reflux d'au moins 20:1 ; et
    (b) faire réagir le flux de fond en présence d'un catalyseur acide pour former un flux de produit comprenant de l'éthylène et/ou de l'éther diéthylique ;
    dans lequel le contaminant contenant de l'azote comprend, ou est, de l'acétonitrile, et la charge d'alimentation constituée d'éthanol comprend 50 ppm en poids ou moins d'azote.
  2. Procédé selon la revendication 1, dans lequel l'étape de distillation de la charge d'alimentation constituée d'éthanol est réalisée à un taux de reflux de 20:1 à 5 000:1, préférablement de 100:1 à 2 000:1, et plus préférablement de 500:1 à 1 500:1.
  3. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'étape de distillation de la charge d'alimentation constituée d'éthanol est réalisée à une pression absolue de 0,02 bar à moins de 2 bars, préférablement de 0,05 bar à 1,5 bar, plus préférablement de 0,1 bar à 1,0 bar, et encore plus préférablement de 0,2 bar à 0,6 bar.
  4. Procédé selon l'une quelconque des revendications précédentes, comprenant en outre l'étape qui consiste à amener le flux de fond à un rebouilleur (203) pour former un flux évaporé (108) et un flux de produit (109), le flux de produit remplaçant le flux inférieur à l'étape (b).
  5. Procédé selon la revendication 4, dans lequel au moins une partie du flux évaporé est recyclée vers l'étape (a) .
  6. Procédé selon l'une quelconque des revendications précédentes, dans lequel la charge d'alimentation constituée d'éthanol est introduite à l'étape (a) à une position intermédiaire entre les positions auxquelles le flux de tête et le flux de fond quittent l'étape (a).
  7. Procédé selon l'une quelconque des revendications précédentes, comprenant en outre l'étape qui consiste à ajouter de l'eau à la charge d'alimentation constituée d'éthanol avant l'étape (a), préférablement dans lequel la quantité d'eau ajoutée est de 0,01 % à 5 %, plus préférablement de 0,5 % à 4 %, encore plus préférablement de 1 % à 3 %, et encore plus préférablement de 1,5 % à 2,5 % en poids, de la charge d'alimentation constituée d'éthanol.
  8. Procédé selon l'une quelconque des revendications précédentes, dans lequel le catalyseur acide comprend un hétéropolyacide, préférablement l'acide silicotungstique.
  9. Procédé selon l'une quelconque des revendications précédentes, dans lequel le catalyseur acide comprend un silicate, préférablement un silicate cristallin ou une zéolite, plus préférablement un silicate cristallin ayant un rapport Si:Al d'au moins 100, un silicate cristallin désaluminisé, ou une zéolite modifiée par le phosphore.
  10. Procédé selon l'une quelconque des revendications précédentes, dans lequel la charge d'alimentation constituée d'éthanol comprend du bioéthanol, ou dans lequel la charge d'alimentation constituée d'éthanol est une charge d'alimentation constituée de bioéthanol.
  11. Procédé selon l'une quelconque des revendications précédentes, comprenant en outre l'étape qui consiste à mettre en contact la charge d'alimentation constituée d'éthanol avec un adsorbant, dans lequel la charge d'alimentation constituée d'éthanol est en phase liquide ou en phase gazeuse, préférablement dans lequel la charge d'alimentation constituée d'éthanol est en phase liquide.
  12. Procédé de préparation d'une charge d'alimentation constituée d'éthanol pour la déshydratation catalysée par un acide d'éthanol pour produire de l'éthylène, le procédé comprenant l'étape qui consiste à distiller une charge d'alimentation constituée d'éthanol (101) comprenant au moins un contaminant contenant de l'azote, dans lequel la distillation a un taux de reflux d'au moins 20:1 et la charge d'alimentation constituée d'éthanol quitte l'étape de distillation dans un flux de fond.
  13. Utilisation d'un procédé selon l'une quelconque des revendications 1 à 11 pour déshydrater une charge d'alimentation constituée d'éthanol appauvrie en contaminants contenant de l'azote, préférablement appauvrie en acétonitrile, en présence d'un catalyseur acide pour produire de l'éthylène et/ou de l'éther diéthylique.
EP14816268.8A 2013-12-24 2014-12-19 Procédé de déshydratation de l'éthanol catalysé par un acide Active EP3087047B1 (fr)

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EP13199602 2013-12-24
EP14816268.8A EP3087047B1 (fr) 2013-12-24 2014-12-19 Procédé de déshydratation de l'éthanol catalysé par un acide
PCT/EP2014/078853 WO2015097100A2 (fr) 2013-12-24 2014-12-19 Procédé de déshydratation de l'éthanol catalysé par un acide

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DK3087047T3 (en) 2018-06-18
US20160326080A1 (en) 2016-11-10
TW201529552A (zh) 2015-08-01
CA2935000C (fr) 2021-08-03
US9828319B2 (en) 2017-11-28
AU2014372702B2 (en) 2019-03-07
KR102371111B1 (ko) 2022-03-07
AR098923A1 (es) 2016-06-22
WO2015097100A3 (fr) 2015-11-26
MX2016008450A (es) 2017-01-11
JP2017507167A (ja) 2017-03-16
CA2935000A1 (fr) 2015-07-02
MY171559A (en) 2019-10-18
CN106132911A (zh) 2016-11-16
TWI647212B (zh) 2019-01-11
RU2016130011A (ru) 2018-01-30
AU2014372702A1 (en) 2016-07-14
TR201806937T4 (tr) 2018-06-21
BR112016014938A2 (pt) 2018-01-23
WO2015097100A2 (fr) 2015-07-02
BR112016014938B1 (pt) 2020-04-14
JP6553084B2 (ja) 2019-07-31
ZA201604268B (en) 2017-07-26
KR20160124081A (ko) 2016-10-26
ES2672006T3 (es) 2018-06-12

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